JP2012041196A - Glass member with sealing material layer, electronic device using the same, and method for producing the electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a glass member with a sealing material layer allowing reduction in occurrence of cracks and splits in a glass substrate and a sealing layer due to laser radiation to the corner of the sealing material layer and reduction in airtightness by bubbling of sealing glass; and to provide an electronic device using the glass member with a sealing material layer.SOLUTION: The glass substrate 3 includes a sealing region 5. The sealing material layer 7, which is formed of a sealing material comprising the sealing glass, a low expansion filling material, and a laser absorbing material, is arranged on the sealing region 5 of the glass substrate 3. The frame-shaped sealing material layer 7 consists of straight line parts 7a and corner parts 7b. In the sealing material layer 7, the width Lof the corner parts 7b is wider than the width Lof the straight line parts 7a.

Description

  The present invention relates to a glass member with a sealing material layer, an electronic device using the same, and a method for manufacturing the same.

  In a flat panel display device (FPD) such as an organic EL display (Organic Electro-Luminescence Display: OELD), a field emission display (Feed Emission Display: FED), a plasma display panel (PDP), a liquid crystal display device (LCD), etc. A structure is applied in which a glass substrate for elements and a glass substrate for sealing, which are formed to face each other, are arranged to face each other and the display element is sealed with a glass package in which these two glass substrates are sealed. Furthermore, in a solar cell such as a dye-sensitized solar cell, it has been studied to apply a glass package in which a solar cell element (dye-sensitized photoelectric conversion element) is sealed with two glass substrates.

  As a sealing material for sealing between two glass substrates, application of sealing glass excellent in moisture resistance or the like is being promoted. However, since the sealing temperature by the sealing glass is about 400 to 600 ° C., the characteristics of the electronic element parts such as organic EL (OEL) elements and solar cell elements are deteriorated when baked using a heating furnace. End up. Therefore, a sealing glass material layer (sealing material layer) including a laser absorbing material is disposed between the sealing regions provided at the periphery of the two glass substrates, and this is irradiated with laser light to be heated and melted. Attempts have been made to form a sealing layer (see Patent Documents 1 and 2). Laser sealing has the advantage that the thermal influence on the electronic element part can be suppressed.

  In a glass package such as an FPD, a rectangular frame-shaped sealing layer is mainly applied in order to enlarge an element region. When laser sealing is applied to the formation of such a sealing layer, the laser beam is continuously irradiated while scanning along the rectangular frame-shaped sealing material layer. The direction (traveling direction) changes by 90 degrees. At the corner portion, the speed at the straight line portion immediately before is rapidly decelerated, and immediately after that, the speed is rapidly accelerated from zero. For this reason, the irradiation time of the laser beam at the corner portion is longer than that at the straight portion, the sealing glass which is the main component of the sealing material layer is excessively heated, and cracks and cracks are generated in the glass substrate and the sealing layer. Or the sealing glass foams and the airtightness is lowered.

  In contrast, Patent Documents 1 and 2 describe that the corner portion of the sealing material layer has an R shape. Although the R-shaped corner portion can reduce the amount of change in the scanning speed of the laser beam as compared with the right-angled corner portion, it is difficult to scan the laser beam at the same speed as the linear portion. If the radius of curvature R of the corner portion is increased, the amount of change in the scanning speed of the laser beam can be reduced, but such a corner portion causes a reduction in the element region. Patent Documents 1 and 2 describe that the laser beam output and the scanning speed are controlled at the corner, but the laser beam irradiation position always moves, so the laser beam irradiation condition (output) And the place where the heating state of the sealing glass is not matched, and cracks and cracks in the glass substrate and the sealing layer, and foaming of the sealing glass are suppressed with good reproducibility. Can not.

Special table 2008-517446 gazette Special table 2008-527657 gazette

  The object of the present invention is to suppress with good reproducibility the cracks and cracks in the glass substrate and sealing layer caused by laser irradiation to the corner of the sealing material layer, and the decrease in airtightness due to foaming of the sealing glass. It is an object to provide a glass member with a sealing material layer, an electronic device using the same, and a method for manufacturing the same.

A glass member with a sealing material layer of the present invention is formed on a glass substrate having a surface having a sealing region, the sealing region of the glass substrate, a sealing glass, a low expansion filler, and a laser absorber. And a sealing material layer-attached glass member comprising a frame-shaped sealing material layer composed of a straight portion and a corner portion having an R shape or a chamfered shape. The corner portion has a width L ₁₂ wider than the straight portion width L _{11 of the} sealing material layer.

An electronic device according to the present invention includes a first glass substrate having a first surface including a first sealing region, and a second surface including a second sealing region corresponding to the first sealing region. A second glass substrate laminated at a predetermined interval on the first glass substrate so that the second surface faces the first surface, and the first glass An electronic element provided between the substrate and the second glass substrate; and the first sealing region of the first glass substrate and the second so as to seal the electronic element. It is formed between the second sealing region of the glass substrate, and is formed of a melt-fixed layer of a sealing material containing a sealing glass, a low expansion filler, and a laser absorbing material, and a linear portion and an R shape or A frame-like sealing layer composed of a corner portion having a chamfered shape, and the straight layer of the sealing layer. Width L ₂₂ of the corner portions than the width L ₂₁ parts are characterized by broad.

The electronic device manufacturing method of the present invention includes a step of preparing a first glass substrate having a first surface including a first sealing region, and a second sealing corresponding to the first sealing region. A region and a fired layer of a sealing material formed on the second sealing region and containing a sealing glass, a low expansion filler, and a laser absorber, and a straight portion and an R shape or a chamfered shape A step of preparing a second glass substrate having a second surface comprising a frame-shaped sealing material layer composed of a corner portion, and the first surface and the second surface are opposed to each other. While laminating the first glass substrate and the second glass substrate through the sealing material layer, the sealing material layer through the first glass substrate or the second glass substrate. The first glass is irradiated with laser light to melt the sealing material layer. And a step of forming a sealing layer which seals the electronic element portion provided between the second glass substrate and the plate, the corner portion than the width L ₁₁ of the straight portion of the sealing material layer width L ₁₂ of the is characterized by wide.

  According to the glass member with the sealing material layer of the present invention and the electronic device using the same and the manufacturing method thereof, cracks and cracks in the glass substrate and the sealing layer caused by laser irradiation to the corner portion of the sealing material layer, Further, it is possible to suppress a decrease in airtightness due to foaming of the sealing glass with good reproducibility. Therefore, it is possible to provide an electronic device excellent in sealing performance, airtightness, reliability thereof, and the like with high reproducibility.

It is sectional drawing which shows the structure of the electronic device by embodiment of this invention. It is sectional drawing which shows the manufacturing process of the electronic device by embodiment of this invention. It is a top view which shows the 1st glass substrate used in the manufacturing process of the electronic device shown in FIG. It is a top view which shows the 2nd glass substrate used at the manufacturing process of the electronic device shown in FIG. It is sectional drawing along the AA line of FIG. It is a top view which expands and shows one structural example of the sealing material layer in the 2nd glass substrate shown in FIG. It is a top view which expands and shows the other structural example of the sealing material layer in the 2nd glass substrate shown in FIG.

  Hereinafter, embodiments for carrying out the present invention will be described with reference to the drawings. 1 is a diagram showing a configuration of an electronic device according to an embodiment of the present invention, FIG. 2 is a diagram showing a manufacturing process of the electronic device according to an embodiment of the present invention, and FIG. 3 is a diagram showing a configuration of a first glass substrate used therefor. 4 and 5 are diagrams showing the configuration of the second glass substrate used therein, and FIGS. 6 and 7 are enlarged views showing a configuration example of the sealing material layer in the second glass substrate.

An electronic device 1 shown in FIG. 1 includes an illuminating device (OEL illumination or the like) using a light emitting element such as an OPD, FED, PDP, or LCD, or a solar cell such as a dye-sensitized solar cell. It constitutes. The electronic device 1 includes a first glass substrate 2 and a second glass substrate 3. The first and second glass substrates 2 and 3 are made of, for example, alkali-free glass or soda lime glass having various known compositions. For example, alkali-free glass has a thermal expansion coefficient of about 30 to 40 × 10 ⁻⁷ / ° C. Soda lime glass has a thermal expansion coefficient of about 80 to 90 × 10 ⁻⁷ / ° C. However, the material of the glass substrates 2 and 3 is not particularly limited.

  An electronic element portion (not shown) corresponding to the electronic device 1 is provided between the surface 2a of the first glass substrate 2 and the surface 3a of the second glass substrate 3 facing it. The electronic element unit is, for example, an OEL element for OELD or OEL illumination, a plasma light emitting element for PDP, a liquid crystal display element for LCD, or a dye-sensitized solar cell element (dye-sensitized photoelectric element for solar cells). Conversion unit element) and the like. An electronic element portion including a display element, a light emitting element, a dye-sensitized solar cell element, and the like has various known structures. The electronic device 1 of this embodiment is not limited to the element structure of the electronic element part.

  The electronic element part in the electronic device 1 is composed of an element film, an electrode film, a wiring film, and the like formed on at least one of the surfaces 2a, 3a of the first and second glass substrates 2, 3. In OELD, FED, PDP, etc., an electronic element part is comprised by the element structure formed in the surface 3a (2a) of one glass substrate 3 (2). In this case, the other glass substrate 2 (3) serves as a sealing substrate, but a filter film or the like may be formed. In addition, in LCDs and dye-sensitized solar cell elements, element films, electrode films, wiring films and the like that form element structures are formed on the surfaces 2a and 3a of the glass substrates 2 and 3, respectively. Is configured.

  As shown in FIG. 3, a first sealing region 4 is provided on the surface 2 a of the first glass substrate 2 used for manufacturing the electronic device 1. On the surface 3a of the second glass substrate 3, a second sealing region 5 corresponding to the first sealing region 4 is provided as shown in FIG. The first and second sealing regions 4 and 5 serve as a sealing layer forming region (a sealing material layer forming region for the second sealing region 5). A portion surrounded by the first and second sealing regions 4 and 5 becomes an element region, and an electronic element portion is provided in the element region.

  The first glass substrate 2 and the second glass substrate 3 have a predetermined gap so that the surface 2a having the first sealing region 4 and the surface 3a having the second sealing region 5 face each other. They are stacked. A gap between the first glass substrate 2 and the second glass substrate 3 is sealed with a sealing layer 6. The sealing layer 6 is formed between the sealing region 4 of the first glass substrate 2 and the sealing region 5 of the second glass substrate 3 so as to seal the electronic element portion. The electronic element portion provided between the first glass substrate 2 and the second glass substrate 3 is a glass panel composed of the first glass substrate 2, the second glass substrate 3, and the sealing layer 6. It is hermetically sealed. The sealing layer 6 has a thickness of about 5 to 200 μm, for example.

  When an OEL element or the like is applied as the electronic element part, a part of the space remains between the first glass substrate 2 and the second glass substrate 3. Such a space may be left as it is, or may be filled with a transparent resin or the like. The transparent resin may be adhered to the glass substrates 2 and 3 or may simply be in contact with the glass substrates 2 and 3. Further, when a dye-sensitized solar cell element or the like is applied as the electronic element part, the electronic element part is disposed in the entire gap between the first glass substrate 2 and the second glass substrate 3.

  The sealing layer 6 is a melt in which the sealing material layer 7 formed on the sealing region 5 of the second glass substrate 3 is melted with a laser beam and fixed to the sealing region 4 of the first glass substrate 2. It consists of a fixed layer. The sealing material layer 7 is melted by local heating using laser light. That is, a frame-shaped sealing material layer 7 is formed in the sealing region 5 of the second glass substrate 3 used for manufacturing the electronic device 1 as shown in FIGS. The sealing material layer 7 formed in the sealing region 5 of the second glass substrate 3 is rapidly heated and rapidly cooled with a laser beam, and is melted and fixed to the sealing region 4 of the first glass substrate 2. A sealing layer 6 that hermetically seals a space (element arrangement space) between the glass substrate 2 and the second glass substrate 3 is formed.

  The sealing material layer 7 is a fired layer of a sealing material (sealing glass material) containing a sealing glass, a low expansion filler, and a laser absorbing material. The sealing material is obtained by blending a laser absorbing material and a low expansion filler into sealing glass as a main component. The sealing material may contain additives other than these as required. For the sealing glass (glass frit), for example, low-melting glass such as tin-phosphate glass, bismuth glass, vanadium glass, lead glass or the like is used. Of these, tin-phosphate glass is used in consideration of sealing properties (adhesiveness) to the glass substrates 2 and 3, reliability thereof (adhesion reliability and sealing properties), and influence on the environment and human body. It is preferable to use sealing glass made of bismuth glass.

Tin-phosphate glass (glass frit) is composed of 20 to 68 mol% SnO, 0.5 to 5 mol% SnO ₂ , and 20 to 40 mol% P ₂ O ₅ (basically a total amount). It is preferable to have a composition of 100 mol%. SnO is a component for lowering the melting point of glass. If the SnO content is less than 20 mol%, the viscosity of the glass will be high and the sealing temperature will be too high, and if it exceeds 68 mol%, it will not vitrify.

SnO ₂ is a component for stabilizing the glass. If the content of SnO ₂ is less than 0.5 mol%, SnO ₂ is separated and precipitated in the glass that has been softened and melted during the sealing operation, the fluidity is impaired and the sealing workability is lowered. If the content of SnO ₂ exceeds 5 mol%, SnO ₂ is likely to precipitate during melting of the low-melting glass. P ₂ O ₅ is a component for forming a glass skeleton. If the content of P ₂ O ₅ is less than 20 mol%, the glass does not vitrify, and if the content exceeds 40 mol%, the weather resistance, which is a disadvantage specific to phosphate glass, may be deteriorated.

Here, the ratio (mol%) of SnO and SnO ₂ in the glass frit can be determined as follows. First, after the glass frit (low melting point glass powder) is acid-decomposed, the total amount of Sn atoms contained in the glass frit is measured by ICP emission spectroscopic analysis. Next, since Sn ²⁺ (SnO) is obtained by acidimetric decomposition, Sn ⁴⁺ (SnO ₂ ) is obtained by subtracting the obtained Sn ²⁺ from the total amount of Sn atoms.

The glass formed of the above three components has a low glass transition point and is suitable for a low-temperature sealing material. However, a component that forms a glass skeleton such as SiO ₂ , ZnO, B ₂ O ₃ , Al _{2 O 3, WO 3, MoO} 3, Nb 2 O 5, TiO 2, ZrO 2, Li 2 O, stabilizing _{Na 2 O, K 2 O,} Cs 2 O, MgO, CaO, SrO, the glass BaO, etc. The component to be made may be contained as an optional component. However, if the content of any component is too large, the glass becomes unstable and devitrification may occur, and the glass transition point and softening point may increase. Therefore, the total content of any component is 30 mol%. The following is preferable. The glass composition in this case is adjusted so that the total amount of the basic component and the optional component is basically 100 mol%.

Bismuth-based glass (gas frit) is composed of 70 to 90% by mass of Bi ₂ O ₃ , 1 to 20% by mass of ZnO, and 2 to 12% by mass of B ₂ O ₃ (basically, the total amount is 100% by mass). It is preferable to have a composition of Bi ₂ O ₃ is a component that forms a glass network. When the content of Bi ₂ O ₃ is less than 70% by mass, the softening point of the low-melting glass becomes high and sealing at a low temperature becomes difficult. When the content of Bi ₂ O ₃ exceeds 90% by mass, it becomes difficult to vitrify and the thermal expansion coefficient tends to be too high.

ZnO is a component that lowers the thermal expansion coefficient and the like. Vitrification becomes difficult when the content of ZnO is less than 1% by mass. When the content of ZnO exceeds 20% by mass, stability during low-melting glass molding is lowered, and devitrification is likely to occur. B ₂ O ₃ is a component that increases the range in which vitrification is possible by forming a glass skeleton. If the content of B ₂ O ₃ is less than 2% by mass, vitrification becomes difficult, and if it exceeds 12% by mass, the softening point becomes too high, and even if a load is applied during sealing, sealing is performed at a low temperature. It becomes difficult.

The glass formed of the above three components has a low glass transition point and is suitable for a sealing material for low temperature. Al ₂ O ₃ , CeO ₂ , SiO ₂ , Ag ₂ O, MoO ₃ , Nb ₂ O ₃ , Ta ₂ O ₅ , Ga ₂ O ₃ , Sb ₂ O ₃ , Li ₂ O, Na ₂ O, K ₂ O, Cs ₂ O, CaO, SrO, BaO, WO ₃ , P ₂ O ₅ , SnO _x (X is 1 or 2) etc. may be contained. However, if the content of any component is too large, the glass becomes unstable and devitrification may occur, and the glass transition point and softening point may increase. Therefore, the total content of any component is 30% by mass. The following is preferable. The glass composition in this case is adjusted so that the total amount of the basic component and the optional component is basically 100% by mass.

  The sealing material contains a laser absorber. As the laser absorbing material, a compound such as at least one metal selected from Fe, Cr, Mn, Co, Ni, and Cu or an oxide containing the metal is used. Moreover, pigments other than these may be used. The content of the laser absorber is preferably in the range of 0.1 to 10% by volume with respect to the sealing material. If the content of the laser absorber is less than 0.1% by volume, the sealing material layer 7 may not be sufficiently melted. If the content of the laser absorbing material exceeds 10% by volume, there is a risk of locally generating heat in the vicinity of the interface with the second glass substrate 3, and the fluidity at the time of melting of the sealing material deteriorates, resulting in the first There exists a possibility that adhesiveness with the glass substrate 2 may fall.

The sealing material further contains a low expansion filler. The low expansion filler is composed of silica, alumina, zirconia, zirconium silicate, aluminum titanate, mullite, cordierite, eucryptite, spodumene, zirconium phosphate compound, quartz solid solution, soda lime glass, and borosilicate glass. It is preferable to use at least one selected from the group. Zirconium phosphate compounds include (ZrO) ₂ P ₂ O ₇ , NaZr ₂ (PO ₄ ) ₃ , KZr ₂ (PO ₄ ) ₃ , Ca _0.5 Zr ₂ (PO ₄ ) ₃ , NbZr (PO ₄ ) ₃ , Zr ₂ (WO ₃ ) (PO ₄ ) ₂ , and complex compounds thereof can be mentioned. The low expansion filler has a lower thermal expansion coefficient than the sealing glass.

The content of the low expansion filler is appropriately set so that the thermal expansion coefficient of the sealing glass approaches the thermal expansion coefficient of the glass substrates 2 and 3. The low expansion filler is preferably contained in the range of 2 to 50% by volume with respect to the sealing material, although it depends on the thermal expansion coefficient of the sealing glass and the glass substrates 2 and 3. When the glass substrates 2 and 3 are formed of alkali-free glass (thermal expansion coefficient: 30 to 40 × 10 ⁻⁷ / ° C.), a relatively large amount (for example, a range of 30 to 50% by volume) of a low expansion filler is used. It is preferable to add. When the glass substrates 2 and 3 are formed of soda lime glass (thermal expansion coefficient: 80 to 90 × 10 ⁻⁷ / ° C.), a relatively small amount (for example, in a range of 2 to 40% by volume) of a low expansion filler is used. It is preferable to add.

  As shown in FIG. 4, the sealing material layer 7 formed in the sealing region 5 of the second glass substrate 3 has a rectangular frame shape including straight portions 7 a and corner portions 7 b. . In addition, the shape of the sealing material layer 7 should just be a frame shape comprised by the linear part 7a and the corner part 7b, and is not limited to a rectangular frame shape. The sealing material layer 7 may have a polygonal shape other than a rectangle. The corner portion 7b has an R shape as shown in FIG. As will be described later, the corner portion 7b may have a chamfered shape (C chamfered shape).

  When the laser beam is irradiated while scanning along the sealing material layer 7 as described above, the scanning direction (traveling direction) of the laser beam changes at the corner portion 7b. In the corner portion 7b having an R shape or a chamfered shape, the scanning speed of the laser light is decelerated from the speed of the straight portion 7a immediately before it, and is accelerated immediately thereafter. For this reason, the irradiation time of the laser beam in the corner part 7b becomes long compared with the linear part 7a. Here, since the content of the laser absorbing material in the sealing material layer 7 is set according to the irradiation condition of the laser beam in the linear portion 7a, the sealing material is used in the corner portion 7b where the irradiation time of the laser beam becomes long. The sealing glass which is the main component of the layer 7 is easily heated excessively. For this reason, there arises a problem that the glass substrates 2 and 3 and the sealing layer 6 are cracked or broken, or that the sealing glass is foamed to reduce the airtightness.

Therefore, in this embodiment, as shown in FIG. 6, the width L ₁₂ of the corner portion 7b of the sealing material layer 7 is made wider than the width L ₁₁ of the straight portion 7a (L ₁₁ <L ₁₂ ). According to such a wide corner portion 7b, since the amount of the sealing material heated by the laser beam, specifically, the amount of the sealing glass increases, excessive heating of the sealing glass is suppressed accordingly. Is done. As shown in FIG. 7, it is the same when the corner portion 7b of the sealing material layer 7 has a chamfered shape, by wider than the width L ₁₁ of the straight portion 7a of the width L ₁₂ of the corner portion 7b, sealing Excessive heating of the glass is suppressed. Accordingly, it is possible to suppress cracks and cracks in the glass substrates 2 and 3 and the sealing layer 6 due to overheating of the sealing glass, and a decrease in airtightness due to foaming of the sealing glass.

Width L ₁₂ of the corner portion 7b of the sealing material layer 7 is preferably set to the width L ₁₁ of the linear portion 7a 1.1 times or more. The width L ₁₂ of the corner portion 7b by a 1.1 L ₁₁ or more, it is possible to reproducibly inhibit excessive heating of the sealing glass at the corner portion 7b. However, there is a risk that insufficient heating too wider than the width L ₁₁ of the straight portion 7a of the width L ₁₂ of the corner portion 7b is caused, adhesion tends to lower at the corner portion 7b. Therefore, the width L ₁₂ of the corner portion 7b is preferably 1.5 times or less the width L ₁₁ of the linear portion 7a. Thus, the width L ₁₂ of the corner portion 7b is preferably in the range of 1.1L ₁₁ ≦ L ₁₂ ≦ 1.5L ₁₁ , and more preferably in the range of 1.2L ₁₁ ≦ L ₁₂ ≦ 1.4L _11. Is more preferable.

Here, when the shape of the corner portion 7b of the sealing material layer 7 is an R shape, by increasing the curvature radii R ₁ and R ₂ inside and outside the corner portion 7b, the laser beam at the corner portion 7b is increased. Speed change can be reduced. However, in such a case, the area of the region surrounded by the sealing material layer 7, that is, the area of the element region forming the electronic element part is greatly reduced. For this reason, it is preferable to make the curvature radius R ₁ inside the corner portion 7b small within a range that does not hinder the smooth scanning of the laser light. Specifically, depending on the width L ₁₁ of the straight portion, the radius of curvature R ₁ of the inner corner portion 7b is preferable to be 10mm or less.

The width L ₁₂ of the corner portion 7b having the R shape indicates a linear distance connecting the center of the inner radius of curvature R ₁ and the imaginary corner portion (intersection of the outer line of the straight portion 7a) as shown in FIG. Shall. The width L ₁₂ of the corner portion 7b to wider than the width L ₁₁ of the straight portion 7a, for example with respect to the radius of curvature of the case where the width L ₁₂ of the corner portion 7b and equal to the width L ₁₁ of the linear portion 7a, The outer radius of curvature R ₂ may be reduced. The outer radius of curvature R ₂ is appropriately set within a range satisfying the above condition of 1.1L ₁₁ ≦ L ₁₂ ≦ 1.5L ₁₁ . The width L ₁₂ of the corner portion 7b having a chamfered shape, it is of the minimum width of the C-chamfered portion formed in a straight line. In this case, by changing the inside or outside of the chamfered shape, it is possible to increase the width L ₁₂ of the corner portion 7b.

As described above, the width L ₁₂ of the corner portion 7b of the sealing material layer 7 is wider than the width L ₁₁ of the linear portion 7a, furthermore 1.1L ₁₁ ≦ L ₁₂ ≦ a width L ₁₂ of the corner portion 7b 1. by a range of 5L _11, while maintaining good adhesion to the glass substrate 2 of the linear portion 7a, it is possible to suppress excessive heating of the corner portion 7b. Therefore, cracks and cracks in the glass substrates 2 and 3 and the sealing layer 6 due to excessive heating of the corner portion 7b of the sealing material layer 7, and a decrease in airtightness due to foaming of the sealing glass are suppressed with good reproducibility. It becomes possible. By these, the glass panel excellent in sealing property, airtightness, etc., and the electronic device 1 can be provided.

  The electronic device 1 of the above-described embodiment is manufactured as follows, for example. First, as shown in FIG. 2A, a first glass substrate 2 and a second glass substrate 3 having a sealing material layer 7 are prepared. The sealing material layer 7 is prepared by mixing a sealing material containing a sealing glass, a low expansion filler, and a laser absorbing material with a vehicle to prepare a sealing material paste, which is used to seal the second glass substrate 3. It is formed by drying and baking after coating on the stop region 5. Specific configurations of the sealing glass, the low expansion filler, and the laser absorber are as described above.

  Vehicles used for the preparation of the sealing material paste include resins such as methylcellulose, ethylcellulose, carboxymethylcellulose, oxyethylcellulose, benzylcellulose, propylcellulose, and nitrocellulose, and solvents such as terpineol, butylcarbitol acetate, and ethylcarbitol acetate. Acrylic resins such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl methacrylate, and the like dissolved in methyl ethyl ketone, terpineol, butyl carbitol acetate, ethyl carbitol acetate Those dissolved in a solvent such as

  The viscosity of the sealing material paste may be adjusted to the viscosity corresponding to the apparatus applied to the glass substrate 3, and can be adjusted by the ratio of the resin (binder component) and the solvent and the ratio of the sealing material and the vehicle. A known additive may be added to the sealing material paste as a glass paste such as an antifoaming agent or a dispersing agent. A known method using a rotary mixer equipped with a stirring blade, a roll mill, a ball mill or the like can be applied to the preparation of the sealing material paste.

The sealing material paste as described above is applied to the sealing region 5 of the glass substrate 3 and dried to form an application layer of the sealing material paste. The sealing material paste is applied onto the second sealing region 5 by applying a printing method such as screen printing or gravure printing, or is applied along the second sealing region 5 using a dispenser or the like. To do. When applying screen printing, wider than the width L ₁₁ of the straight portion 7a of the width L ₁₂ of the corner portion 7b on the basis of the screen pattern. Also, when applied using a dispenser or the like, by controlling the discharge pressure and coating speed, etc., it is wider than the width L ₁₁ of the straight portion 7a of the width L ₁₂ of the corner portion 7b.

The coating layer of the sealing material paste is preferably dried, for example, at a temperature of 120 ° C. or higher for 10 minutes or longer, whereby the solvent in the coating layer can be sufficiently removed. If the solvent remains in the coating layer, the binder component may not be sufficiently removed in the subsequent firing step. The sealing material layer 7 is formed by baking the coating layer of the sealing material paste. In the firing step, the coating layer is first heated to a temperature below the glass transition point of the sealing glass (glass frit), which is the main component of the sealing material, the binder component in the coating layer is removed, and then the sealing glass is softened. The sealing material is melted and baked on the glass substrate 3 by heating to a temperature above the point. In this manner, the width L ₁₂ of the corner portion 7b to form a broad sealing material layer 7 than the width L ₁₁ of the linear portion 7a.

  Next, as shown in FIG.2 (b), the 1st glass substrate 2 and the 2nd glass substrate 3 are laminated | stacked through the sealing material layer 7 so that those surfaces 2a and 3a may oppose. To do. Next, as shown in FIG. 2C, the sealing material layer 7 is irradiated with laser light 8 through the second glass substrate 3 (or the first glass substrate 2). The laser beam 8 is irradiated while scanning along the frame-shaped sealing material layer 7. The laser light is not particularly limited, and laser light from a semiconductor laser, carbon dioxide laser, excimer laser, YAG laser, HeNe laser, or the like is used.

When irradiating a laser beam 8 to the sealing material layer 7, since the greater than the width L ₁₁ of the straight portion 7a of the width L ₁₂ of the corner portion 7b of the sealing material layer 7, the laser beam 8 changes the output or the like Irradiation can be performed under certain conditions. However, it is preferable that the width L ₁₂ of the corner portion 7 b be equal to or smaller than the spot diameter D of the laser beam 8 (L ₁₂ ≦ D). When the width L ₁₂ of the corner portion 7b is wider than the spot diameter D of the laser beam 8, melt defects such as the sealing material layer 7 is likely to occur. In order to melt the corner portion 7 b more stably, the width L ₁₂ of the corner portion 7 b preferably satisfies the relationship of 0.6D ≦ L ₁₂ ≦ 0.9 D with respect to the spot diameter D of the laser beam 8.

The sealing material layer 7 is melted sequentially from the portion irradiated with the laser light 8 scanned along the sealing material layer 7, and is rapidly cooled and solidified and fixed to the first glass substrate 2 at the end of the irradiation of the laser light 8. Then, by irradiating the entire circumference of the sealing material layer 7 with the laser beam 8, as shown in FIG. 2 (d), the seal between the first glass substrate 2 and the second glass substrate 3 is sealed. The wearing layer 6 is formed. Although the width of the sealing layer 6 slightly varies from the width of the sealing material layer 7, the corner width L ₂₂ is wider than the straight portion width L ₂₁ based on the shape of the sealing material layer 7. Further, regarding the specific width, the width L ₂₂ of the corner portion of the sealing layer 6 is in the range of 1.1 to 1.5 times the width L _{21 of the} straight portion (1.1L ₂₁ ≦ L ₂₂ ≦ 1.5L ₂₁ ) is preferable.

  In this way, a glass panel constituted by the first glass substrate 2, the second glass substrate 3 and the sealing layer 6 is arranged between the first glass substrate 2 and the second glass substrate 3. The electronic device 1 in which the electronic element portion is hermetically sealed is manufactured. In addition, the glass panel of this embodiment is not restricted to the component of the electronic device 1, It is possible to apply also to glass members (building materials etc.), such as a sealing body of electronic components, or multilayer glass. is there.

  According to the electronic device 1 of this embodiment and the manufacturing process thereof, the glass substrate 2, 3 and the sealing layer 6 are cracked or cracked due to the irradiation of the laser beam 8 to the corner portion 7b of the sealing material layer 7, or Reduction in airtightness due to foaming of the sealing glass is suppressed with good reproducibility. Therefore, the yield of the laser sealing process of the electronic device 1 (glass panel) can be increased, and the airtightness and reliability of the electronic device 1 (glass panel) can be improved. As a result, the electronic device 1 having excellent reliability can be manufactured with a high yield.

  Next, specific examples of the present invention and evaluation results thereof will be described. In addition, the following description does not limit this invention, The modification | change in the form along the meaning of this invention is possible.

Example 1
First, tin-phosphate glass frit (softening point: 401 ° C.) having a composition of 63 mol% SnO, ₂ mol% SnO ₂ , 29 mol% P ₂ O _{5, 5} mol% ZnO, and 1 mol% SiO ₂ , low Zirconium phosphate powder having an average particle diameter (D50) of 3 μm as an expansion filler and a composition of 35 mass% Fe ₂ O ₃ -35 mass% Cr ₂ O ₃ -20 mass% Co ₂ O ₃ -10 mass% MnO A laser absorber having an average particle diameter (D50) of 2 μm was prepared.

A sealing material (thermal expansion coefficient: 45 × 10 ⁻⁷ / ° C.) is prepared by mixing 51 volume% of the tin-phosphate glass frit described above, 45 volume% of zirconium phosphate powder, and 4 volume% of the laser absorber. did. Next, 80% by mass of the sealing material was mixed with 20% by mass of the vehicle to prepare a sealing material paste. The vehicle was prepared by dissolving 4% by mass of nitrocellulose as a binder component in 96% by mass of a solvent composed of butyl carbitol acetate.

Next, a second glass substrate (dimension: 90 × 90 × 0.7 mmt) made of alkali-free glass (thermal expansion coefficient: 38 × 10 ⁻⁷ / ° C.) is prepared and sealed in a sealing region of this glass substrate. The coating material paste was applied by screen printing and then dried under conditions of 130 ° C. × 5 minutes. Such a coating layer was baked under conditions of 430 ° C. × 10 minutes to form a sealing material layer having a film thickness of 31 μm. The overall shape of the sealing material layer (the shape after firing the coating layer of the sealing material paste) is a rectangular frame (outer shape: long side 70 mm × short side 50 mm), and the straight portion width L ₁₁ is 1.1 mm. It was. Each corner portion has an R shape, the inner radius of curvature R ₁ is 1.6 mm, and the outer radius of curvature R ₂ is 1.0 mm. The corner portion width L ₁₂ is 1.31 mm.

The second glass substrate having the sealing material layer described above and the first glass substrate having the element region (a substrate made of non-alkali glass having the same composition and shape as the second glass substrate) are used as the sealing material layer. Laminated. Next, the sealing material layer is irradiated with a laser beam (semiconductor laser) having a wavelength of 940 nm, an output of 30 W, and a spot diameter D of 2 mm through the second glass substrate at a scanning speed of 10 mm / s. The first glass substrate and the second glass substrate were sealed by melting and rapid solidification. The width L ₂₁ of the straight portion of the sealing layer is 1.1 mm, and the width L _{22 of the} corner portion is 1.3 mm. In this way, the electronic device in which the element region was sealed with the glass panel was subjected to the characteristic evaluation described later.

(Examples 2 to 4)
Except for changing the shape of the corner portion of the sealing material layer to the conditions shown in Table 1, in the same manner as in Example 1, the step of forming the sealing material layer on the second glass substrate, the first glass substrate and the first glass substrate The laser sealing process with 2 glass substrates was implemented, and the electronic device which sealed each element area | region with the glass panel was produced. Each electronic device (glass panel) was subjected to characteristic evaluation described later.

(Comparative Example 1)
Except for changing the shape of the corner portion of the sealing material layer to the conditions shown in Table 1, in the same manner as in Example 1, the step of forming the sealing material layer on the second glass substrate, the first glass substrate and the first glass substrate The laser sealing process with 2 glass substrates was implemented, and the electronic device which sealed each element area | region with the glass panel was produced. Each electronic device (glass panel) was subjected to characteristic evaluation described later.

  Next, about the external appearance of the glass panel of Examples 1-4 and the comparative example 1, the substrate crack and the crack of the sealing layer in the time of completion | finish of laser beam irradiation were evaluated. The appearance was evaluated by observing the straight part and the corner part of the sealing layer using an optical microscope. Moreover, the airtightness of each glass panel was measured. The airtightness was evaluated by applying a helium leak test. These measurement and evaluation results are shown in Table 1 together with the manufacturing conditions of the glass panel.

  As is clear from Table 1, all of the glass panels according to Examples 1 to 3 were excellent in appearance and airtightness, and no defects due to corner portions were observed. In Example 4, insufficient cornering was observed at the corner, but this lack of adhesion was resolved by increasing the laser beam output by, for example, about 10% or decreasing the laser beam scanning speed by, for example, about 10%. It is considered that a good sealing state can be obtained. On the other hand, in Comparative Example 1, cracks and foaming due to excessive heating of the corner portions were observed. In the glass panel of Comparative Example 1, no airtightness was obtained.

(Example 5)
Bismuth glass frit (softening point: 420 ° C.) having a composition of 82% by mass of Bi ₂ O ₃ , 11% by mass of ZnO, 6% by mass of B ₂ O _{3 and} 1% by mass of Al ₂ O _3, and average as a low expansion filler It has a cordierite powder having a particle size (D50) of 1 μm, a composition of 35 mass% Fe ₂ O ₃ -35 mass% Cr ₂ O ₃ -20 mass% Co ₂ O ₃ -10 mass% MnO, and an average particle diameter ( A laser absorber having a D50) of 2 μm was prepared.

A sealing material (thermal expansion coefficient: 82 × 10 ⁻⁷ / ° C.) was prepared by mixing 77% by volume of the bismuth-based glass frit, 19% by volume of cordierite powder, and 4% by volume of the laser absorber. Next, 84% by mass of the sealing material was mixed with 16% by mass of the vehicle to prepare a sealing material paste. The vehicle was prepared by dissolving 3% by mass of nitrocellulose as a binder component in 97% by mass of a mixed solvent of terpineol (48% by mass) and butyl carbitol acetate (58% by mass).

Next, a second glass substrate (dimensions: 100 × 100 × 1.8 mmt) made of soda lime glass (thermal expansion coefficient: 83 × 10 ⁻⁷ / ° C.) is prepared and sealed in a sealing region of the glass substrate. The coating material paste was applied by screen printing and then dried under conditions of 130 ° C. × 5 minutes. Such a coating layer was baked under conditions of 430 ° C. × 10 minutes to form a sealing material layer having a thickness of 22 μm. The overall shape of the sealing material layer (the shape after firing the coating layer of the sealing material paste) is a rectangular frame (outer shape: long side 70 mm × short side 50 mm), and the straight portion width L ₁₁ is 0.6 mm. It was. Each corner has an R shape, the inner radius of curvature R ₁ is 4.8 mm, and the outer radius of curvature R ₂ is 5 mm. The corner portion width L ₁₂ is 0.77 mm.

The second glass substrate having the sealing material layer described above and the first glass substrate having the element region (a substrate made of non-alkali glass having the same composition and shape as the second glass substrate) are used as the sealing material layer. Laminated. Next, the sealing material layer is irradiated with a laser beam (semiconductor laser) having a wavelength of 940 nm, an output of 35 W, and a spot diameter D of 1 mm through the second glass substrate at a scanning speed of 20 mm / s. The first glass substrate and the second glass substrate were sealed by melting and rapid solidification. The width L ₂₁ of the straight portion of the sealing layer is 0.6 mm, and the width L _{22 of the} corner portion is 0.8 mm. In this way, the electronic device in which the element region was sealed with the glass panel was subjected to the characteristic evaluation described later.

(Examples 6 to 7)
Except for changing the shape of the corner portion of the sealing material layer to the conditions shown in Table 2, in the same manner as in Example 5, the step of forming the sealing material layer on the second glass substrate, the first glass substrate and the first glass substrate The laser sealing process with 2 glass substrates was implemented, and the electronic device which sealed each element area | region with the glass panel was produced. Each electronic device (glass panel) was subjected to characteristic evaluation described later.

(Comparative Example 2)
Except for changing the shape of the corner portion of the sealing material layer to the conditions shown in Table 2, in the same manner as in Example 5, the step of forming the sealing material layer on the second glass substrate, the first glass substrate and the first glass substrate The laser sealing process with 2 glass substrates was implemented, and the electronic device which sealed each element area | region with the glass panel was produced. Each electronic device (glass panel) was subjected to characteristic evaluation described later.

  Next, with respect to the appearance of the glass panels of Examples 5 to 7 and Comparative Example 2, the substrate cracks and the cracks of the sealing layer at the end of the laser beam irradiation were evaluated. The appearance was evaluated by observing the straight part and the corner part of the sealing layer using an optical microscope. Moreover, the airtightness of each glass panel was measured. The airtightness was evaluated by applying a helium leak test. These measurement and evaluation results are shown in Table 2 together with the manufacturing conditions of the glass panel.

  As is clear from Table 2, all the glass panels according to Examples 5 to 6 were excellent in appearance and airtightness, and no defects due to corner portions were observed. In Example 7, insufficient adhesion was observed at the corner, but this insufficient adhesion was resolved by increasing the laser beam output by, for example, about 10% or decreasing the laser beam scanning speed by, for example, about 10%. It is considered that a good sealing state can be obtained. On the other hand, in Comparative Example 2, cracks and foaming due to excessive heating of the corner portions were observed. In the glass panel of Comparative Example 1, no airtightness was obtained.

  DESCRIPTION OF SYMBOLS 1 ... Electronic device, 2 ... 1st glass substrate, 2a ... Surface, 3 ... 2nd glass substrate, 3a ... Surface, 4 ... 1st sealing area | region, 5 ... 2nd sealing area | region, 6 ... Sealing Adhesion layer, 7 ... sealing material layer, 8 ... laser beam.

Claims (11)

A glass substrate having a surface with a sealing region;
A corner formed on the sealing region of the glass substrate and made of a fired layer of a sealing material containing sealing glass, a low expansion filler and a laser absorber, and having a straight portion and an R shape or a chamfered shape A glass member with a sealing material layer comprising a frame-shaped sealing material layer composed of a portion,
A glass member with a sealing material layer, wherein a width L _{12 of the} corner portion is wider than a width L _{11 of the} straight portion of the sealing material layer. The width L _{12 of the} corner portion of the sealing material layer satisfies a relationship of 1.1L ₁₁ ≦ L ₁₂ ≦ 1.5L ₁₁ with respect to the width L _{11 of the} linear portion. The glass member with a sealing material layer as described.   The sealing material comprises 0.1 to 10% by volume of the laser absorber made of at least one metal selected from the group consisting of Fe, Cr, Mn, Co, Ni, and Cu or a compound containing the metal. The glass member with a sealing material layer according to claim 1, wherein the glass member is contained in a range.   The sealing material is made of silica, alumina, zirconia, zirconium silicate, aluminum titanate, mullite, cordierite, eucryptite, spodumene, zirconium phosphate compound, quartz solid solution, soda lime glass, and borosilicate glass. The glass member with a sealing material layer according to any one of claims 1 to 3, wherein the low-expansion filler consisting of at least one selected from 2 to 50% by volume is contained.   The glass member with a sealing material layer according to any one of claims 1 to 4, wherein the sealing glass is made of tin-phosphate glass or bismuth glass. A first glass substrate having a first surface with a first sealing region;
The first glass substrate has a second surface including a second sealing region corresponding to the first sealing region, and the second surface faces the first surface. A second glass substrate laminated at a predetermined interval;
An electronic element unit provided between the first glass substrate and the second glass substrate;
A sealing glass formed between the first sealing region of the first glass substrate and the second sealing region of the second glass substrate so as to seal the electronic element portion. And a frame-shaped sealing layer composed of a linear portion and a corner portion having an R shape or a chamfered shape, and a melt-fixed layer of a sealing material containing a low expansion filler and a laser absorber. And
An electronic device characterized the width L ₂₂ of the corner portion is wider than the width L ₂₁ of the linear portion of the sealing layer. The width L _{22 of the} corner portion of the sealing layer satisfies a relationship of 1.1L ₂₁ ≦ L ₂₂ ≦ 1.5L ₂₁ with respect to the width L _{21 of the} linear portion. Electronic devices. Providing a first glass substrate having a first surface with a first sealing region;
A second sealing region corresponding to the first sealing region; and a sealing material formed on the second sealing region and including a sealing glass, a low expansion filler, and a laser absorbing material. A step of preparing a second glass substrate having a second surface comprising a fired layer and having a frame-shaped sealing material layer composed of a linear portion and a corner portion having an R shape or a chamfered shape;
Laminating the first glass substrate and the second glass substrate through the sealing material layer while facing the first surface and the second surface;
The sealing material layer is irradiated with laser light through the first glass substrate or the second glass substrate, and the sealing material layer is melted to form the first glass substrate and the second glass substrate. And a step of forming a sealing layer for sealing an electronic element portion provided therebetween,
The method for manufacturing an electronic device, wherein a width L _{12 of the} corner portion is wider than a width L _{11 of the} straight portion of the sealing material layer. The width L _{12 of the} corner portion of the sealing material layer satisfies a relationship of 1.1L ₁₁ ≦ L ₁₂ ≦ 1.5L ₁₁ with respect to the width L _{11 of the} linear portion. The manufacturing method of the electronic device of description. 10. The method of manufacturing an electronic device according to claim 8, wherein a width L _{12 of the} corner portion of the sealing material layer is equal to or smaller than an irradiation spot diameter D of the laser light. The width L _{12 of the} corner portion of the sealing material layer satisfies a relationship of 0.6D ≦ L ₁₂ ≦ 0.9D with respect to an irradiation spot diameter D of the laser light. 9. A method for manufacturing an electronic device according to 9.

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